<<-2-yl)methyl>carbonyl>oxy>-2(1H)-pyridinethione

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚满类
• 英文名称: <<-2-yl)methyl>carbonyl>oxy>-2(1H)-pyridinethione
• 英文别名: ({[trans-(spiro[cyclopropane-1,1'-indan]-2-yl)methyl]carbonyl}oxy)-2(1H)-pyridinethione；(2-sulfanylidenepyridin-1-yl) 2-[(1'R,3S)-spiro[1,2-dihydroindene-3,2'-cyclopropane]-1'-yl]acetate
• 化学式: C₁₈H₁₇NO₂S
• 分子量: 311.404
• InChiKey: NIYVHAJNQRRYRH-KSSFIOAISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  61.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  在 4-二甲氨基吡啶 、 草酰氯 、 N,N-二甲基甲酰胺 作用下， 以 苯 为溶剂， 反应 16.0h， 生成 <<-2-yl)methyl>carbonyl>oxy>-2(1H)-pyridinethione
  参考文献：
  名称：

  Picosecond Radical Kinetics. Fast Ring Openings of Constrained, Aryl-Substituted Cyclopropylcarbinyl Radicals

  摘要：

  The kinetics of ring openings of the exo- and endo-(2,3-benzobicyclo [3.1.0]hex-2-en-6-yl)methyl radicals (4a and 5a), the trans-(spiro[cyclopropane-1,1'-indan]-2-yl)methyl radical (6a), and the (spiro[cyclopropane-1,9'-fluorene]-2-yl)methyl radical (7a) have been studied by competition kinetics employing benzeneselenol trapping. Arrhenius functions for ring openings were determined for reactions conducted between -80 and 50 degrees C. Each radical rearranges rapidly, with rate constants at 25 degrees C of 3 x 10(11) (4a), 2 x 10(11) (5a), 6 x 10(11) (6a), and 6 x 10(12) s(-1) (7a). Precursors to these radicals represent hypersensitive mechanistic probes with unambiguous rate constants for rearrangement. The results confirm the utility of a previously employed semiquantitative method for estimating rate constants for aryl-substituted cyclopropylcarbinyl rearrangements based on Marcus theory. However, they also show that severe dihedral angles between the aromatic pi-systems and the breaking cyclopropyl C-C bonds in the energy-minimized structures cannot be used to predict kinetic effects in the rearrangement reactions. The ramifications of the kinetic results for mechanistic studies of enzyme-catalyzed oxidations of hydrocarbons that employed hypersensitive probes are discussed.

  DOI：

  10.1021/ja00099a036

文献信息

• Picosecond Radical Kinetics. Fast Ring Openings of Constrained, Aryl-Substituted Cyclopropylcarbinyl Radicals
  作者：Amanda A. Martin-Esker、Cathy C. Johnson、John H. Horner、Martin Newcomb

  DOI：10.1021/ja00099a036

  日期：1994.10

  The kinetics of ring openings of the exo- and endo-(2,3-benzobicyclo [3.1.0]hex-2-en-6-yl)methyl radicals (4a and 5a), the trans-(spiro[cyclopropane-1,1'-indan]-2-yl)methyl radical (6a), and the (spiro[cyclopropane-1,9'-fluorene]-2-yl)methyl radical (7a) have been studied by competition kinetics employing benzeneselenol trapping. Arrhenius functions for ring openings were determined for reactions conducted between -80 and 50 degrees C. Each radical rearranges rapidly, with rate constants at 25 degrees C of 3 x 10(11) (4a), 2 x 10(11) (5a), 6 x 10(11) (6a), and 6 x 10(12) s(-1) (7a). Precursors to these radicals represent hypersensitive mechanistic probes with unambiguous rate constants for rearrangement. The results confirm the utility of a previously employed semiquantitative method for estimating rate constants for aryl-substituted cyclopropylcarbinyl rearrangements based on Marcus theory. However, they also show that severe dihedral angles between the aromatic pi-systems and the breaking cyclopropyl C-C bonds in the energy-minimized structures cannot be used to predict kinetic effects in the rearrangement reactions. The ramifications of the kinetic results for mechanistic studies of enzyme-catalyzed oxidations of hydrocarbons that employed hypersensitive probes are discussed.